Sciencemadness Discussion Board

Octanitrocubane

APO - 5-8-2013 at 10:52

Here is a quick scheme I made on a possible synthesis for Cubane Tetracarboxylicchloride which is a precursor to Tetranitrocubane which is a precursor to Heptanitrocubane and finally Octanitrocubane:


<img src="http://www.aposma.host56.com/Cubane.jpg" width="900" />


I don't know if it will work, since I modified it quite a bit, so I would like input on any problematic areas. This is based off of various cubane syntheses, and my own modifications. Nothing shown is mean't to be stoichiometric. Also, could Nitryl Chloride be added to Cubane Dicarboxylic Acid or Cubane Tetracarboxylicchloride to nitrosate it to Octanitrocubane in one shot?

References:

http://www.synarchive.com/syn/14
http://www.synarchive.com/syn/189
http://www.ch.ic.ac.uk/local/projects/b_muir/Cubane/Cubanepr...
https://sites.google.com/site/energeticscribble/comparison-w...
Attachment: Dimethyl Cubane-1,4-Dicarboxylate.pdf (305kB)
This file has been downloaded 591 times

[Edited on 5-8-2013 by APO]

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Dany - 5-8-2013 at 12:08

the first obvious problem is in the last step: I don't know how you create two more carbon atoms when refluxing with thionyl chloride!

and no you can't put NOCl to nitrate it to ONC. first you have two electrophilic species: your acyl chloride and NOCl. you need a nucleophile and electrophile. in fact if you succeed to synthesize the molecule (1,3,5,7-tetraacylchloride) you may in theory reacted with NaN3 that will form the azido derivative (addition-elemination on acyl group). by heating the resulting acylazide, you will induce a Curtis rearrangement forming a tetraisocyanate. oxidizing tetraisocyanate with DMDO (Dimethyldioxirane) you will transform the tetraisocyanate to 1,3,5,7-tetranitrocubane. next, nitrating the tetranitro derivatives need to create a carbanion on the adjacent carbon (carbon adjacent to nitro-bearing carbon) wich is the methode of Eaton et al. the formation of this carbanion by sodium HEXAMETHYLDISILAZANE ( same procedure of Eaton) is possible because the cubyl carbon is relatively acid (presence of electroattracting nitro group next to him). in fact Eaton did an "interfacial nitration" with N2O4 at low temperature, the step are repeated to to achieve ONC.

but you must put in mind that only one synthesis has been published, and maybe the result of Eaton et al. are not reproducible.

what is disappointing abou ONC is that all methods used (empirical, semi-empirical and theoretic) fail to predict the correct crystallin density wich appear less than predicted. The scientist hope that is another more dense polymorph yet to discover. this is done by recrystallisation of ONC by various solvent.

i think the most promising and fastest method for synthesizing ONC is by tetraoligomerization of dinitroacetylene. Unfortunately, dinitroacetylene is unstable. recently Philip PAGORIA of the Lawrence Livermore National Laboratory (LLNL) succeed in the isolation of a stable form of mononitroacetylene (in the form of binuclear complexe of cobalt carbonyl). another metastable derivative of mononitroacetylene is the silylated one. but this compound decompose in solution.
you may need to read the following interesting paper

"En route to dinitroacetylene: nitro(trimethylsilyl)acetylene and nitroacetylene harnessed by dicobalt hexacarbonyl"
Windler GK, Zhang MX, Zitterbart R, Pagoria PF, Vollhardt KP.

Dany.

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bfesser - 5-8-2013 at 12:15

<strong>APO</strong>, you've provided zero references. How do you expect this to be taken seriously?

APO - 5-8-2013 at 13:44

Bfesser, just added my source material. Dany, I fixed the last part, it was actually Phosgene, not Thionyl Chloride. Also Nitryl Chloride is NO2Cl, not NOCl. Could Nitryl Chloride be used instead of Nitrosyl Chloride and Ozone for converting Heptanitrocubane to Octanitrocubane though?

Dany - 5-8-2013 at 13:50

what i am sure is that the last step is wrong. you cannot introduce an acyl chloride just by heating this substrat with phosgene. This reaction may be done photochemically.

this is an old reference for synthesizing cyclohexanoyl chloride from cyclohexane and phosgene. of course the reaction is a photochemical one.

THE PHOTOCHEMICAL REACTIONS OF OXALYL CHLORIDE AND PHOSGENE WITH CYCLOHEXANE (J. Am. Chem. Soc., 1940, 62 (2), pp 454–454).

Dany.

APO - 5-8-2013 at 14:09

Fixed the last part, again.

Dany - 5-8-2013 at 14:21

Let me give you an advice in Organic chemistry. you can amuse yourself all the day by drawing theoretical organic scheme on board. In reality, what may seem logical on a paper may not work at all in Lab. to be a serious chemist and scientist, theoretical calculation should be done on every reaction using for example DFT (Density Functional Theory) to calculate the energy of each intermediate and predict the most plausible transition state, or simply trying the reaction in a lab under different conditions. i gave you the example of cyclohexane just for information. Cubyl systems have different reactivity and are not simple cycloalkane. you cannot simply copy-past a reaction condition from substrate to another! Yes, you can make this for fun but you drawing are uncertain and only informative.

Dany.

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APO - 5-8-2013 at 15:04

I know... I'm just curious if this synth will work.

Motherload - 7-8-2013 at 20:50

Did you not read Dany's post.
That should answer your question.

APO - 7-8-2013 at 23:22

Just implying it may not work, is not informative enough. I would like to know specific reasons why. Just answer if it were done under proper conditions if these reactions would work to produce the specified compounds.

Dany - 8-8-2013 at 05:00

Hello APO,
The scientific answer to your question is that this synthesis work for the cuban 1,4-dicarboxylic acid because it is already published. beyound this step you cannot predict (just by sitting in front of you PC) the outcom of the reaction (for the formation cuban 1,3,5,7-tetracarboxilic acid). The prediction will be uncertain. This should be done experimentally (or theoretically, using reliable model for this system). Just an important remark: although the synthesis of the cuban 1,4-dicarboxylic acid is published, result may not be reproducible. in fact one of the major problem in organic chemistry is that many published work are not reproducible. the reason is that the authors of published paper have omitted this point (reproducibility) so as they can publish in high impact factor journal. for the same reason (publishing in high impact factor) the authors may not telling the truth about the real yield. So you may want to synthesis a compound already descibed in the literature, and you will realize that some reaction give low yield, significally lower from the published yield. but at the same time reaction yield depend also on the operator, reagents and purity.

Dany.

Full Octanitrocubane Synthesis

APO - 8-10-2013 at 16:27

<img src="http://www.apo.comule.com/ONC.jpg" width="666" height="370">


Above is my revised synthesis of Octanitrocubane, all these reactions have been stitched together from various synthesis diagrams. As you can see I added some extra notes about nitration workup. I'm not including my written procedure yet as I've only covered the steps up to Cubane Dicarboxylic Acid. Here's pretty much what is happening, note that I've only included the main reactions, no workup included or detailed reactions conditions or reagent specifications. This is just to give a rough idea of what all this would be like.

Cyclopentanone reacts with Ethylene Glycol using Toluene Sulfonic Acid acid as a catalyst and Toluene as an azeotroping agent while refluxing for thirty hours using a barret type dean-stark trap to remove water. Once the Acid-Catalysed Ketalization is finished the Cyclopentanone Ethylene Ketal formed is then Brominated by adding elemental Bromine dropwise to a solution of it in Dioxane and stirring it for two days. After Bromination, the Tribromocyclopentanone Ethylene Ketal formed undergoes partial Dehydrohalogenation and Dimerization by the Diels-Alder Reaction, this is done by refluxing in a solution of Methanol and Sodium Hydroxide for two hours. Then the Bisethylene Ketal groups on the Dibromodicyclopentadienedione Bisethylene Ketal created are hydrolysed off by stirring with Sulfuric Acid for thirty and a half hours. The Dibromodicyclopentadienedione produced undergoes photocatalyzed cage formation by reacting with Methanol, and aqueous Hydrochloric Acid while being irradiated by a Mercury lamp the duration of the reaction depends on the lamps output. Then the new cage formed undergoes the Favorskii Rearrangement by refluxing in aqueous Sodium Hydroxide and acidifying with Hydrochloric Acid to form Cubane Dicarboxylic Acid. The Cubane Dicarboxylic Acid is then refluxed with Thionyl Chloride for two hours to form Cubane Dicarboxylic Chloride. The new product made is then reacted with Oxalyl Chloride while being irradiated with a Mercury lamp to form Cubane Tetracarboxylic Chloride, again the duration of the reaction depends on the lamps power. The Cubane Tetracarboxylic Chloride is then reacted with Trimethylsilyl Azide to form the Tetracarboxylic Azide, and then heated to form the Tetraisocyanate. Then the Cubane Tetraisocyanate formed is Hydrolyzed with water to form Cubane Tetraamine. The Amine groups on the Cubane Tetraamine are oxidized with Dimethyldioxirane to form Tetranitrocubane. The Tetranitrocubane then undergoes interfacial nitration, first it is cooled, and Sodium Bistrimethylsilyl Amide is added to the Tetranitrocubane in a solution of Tetrahydrofuran and Methyl Tetrahydrofuran, then it is cooled further and Dinitrogen Tetroxide in cold Isopentane is added dropwise to form Heptanitocubane. Finally the Heptanitrocubane is added to Lithium Bistrimethylsilyl Amide in Dichloromethane to form the Lithium salt. The Lithium salt of Heptanitrocubane is then reacted with Nitrosyl Chloride to form Nitrosoheptanitrocubane and then with Ozone to oxidize the Nitroso group to a Nitro group, giving Octanitrocubane.

Now I have a couple questions, could Dimethyldioxirane be replaced with Peroxymonosulfuric Acid for converting the Cubane Tetraamine to Tetranitrocubane? Several threads here and various internet sources describe it's use for oxidizing Amine groups to Nitro groups, which is exactly what Dimethyldioxirane is used for. I think it would be easier to use than Dimethyldioxirane since, while both must be prepared immediately prior to use, the production of Dimethyldioxirane while cheap, gives very low yield and requires an elaborate setup, immediate titration and cold temperature. Peroxymonosulfuric Acid, while somewhat dangerous, it is very easy to prepare on site, just mixing two things together, no big deal. Now for my second question, could Nitryl Chloride could be used in place of Nitrosyl Chloride and Ozone to nitrate the final position on the Cubane? Just to simplify the process a little, and because Ozone is quite difficult to produce in significant quantity.


Here are my sources:

Applications of Cubane

Further Cubane Topics

Cubane Reactivity

Multiple Cubane Synthesis

Trinitro and Tetranitro Cubane Synthesis

Improved Tetranitrocubane Synthesis

Pentanitro and Hexanitro Cubane Synthesis

Heptanitro and Octanitrocubane Synthesis

Properties of Heptanitro and Octanitrocubane

Philip E. Eaton Synthesis of Cubane

John Tsanaktsidis Synthesis of Cubane

Octanitrocubane Synthesis Overview

Cubane Derivitives for Propellant Applications

Dimethyl Cubane-1,4-Dicarboxylate: A Practical Laboratory Scale Synthesis

Design and Synthesis of Explosives: Polynitrocubanes and High Nitrogen Content Heterocycles


All input is appreciated, especially literature, answers, and related. Any documents describing procedures of anysort would be awesome.

Thanks.

Dany - 8-10-2013 at 19:04

Hello APO,

once again you return to octanitrocubane (ONC). So this time i see that your synthesis will stop at the 11th step (formation of the tetraaminocubane). In your case you cannot form tetranitrocubanes from the corresponding tetraaminocubane because your amino group are adjacent and thus, ring cleavage will occurs . This is the same problem that Eaton et al. faced during the synthesis of ONC. below i copied from [1] what Eaton says about the oxidation of adjacent amino groups to nitro on a cubane scaffold:

"...There is nothing wrong with this, even on the cubane skeleton; 1,2-diaminocubanes have been made. They are relatively stable compounds, but ring cleavage reactions intervene during attempted oxidation to the corresponding 1,2-dinitrocubane. This sort of skeletal cleavage always happens when attempts are made to place an electrondonating group (e.g. NH2) on a cubane carbon adjacent to one bearing an electron-withdrawing substituent (e.g.NO2). It is unavoidable and is one of the very few limitations imposed on manipulation of substitution/substitution pattern in the cubanes"

So if your are lucky and the synthesis work, probably the farthest compound you can make is the tetraaminocubane (i didn't check the previous steps, but the step of oxidation of the tetraaminocubane to the corresponding tetranitro will not work).

Reference:

[1] Philip E. Eaton, Mao-Xi Zhang, Richard Gilardi, Nat Gelber , Sury Iyer, Rao Surapaneni, Octanitrocubane: A New Nitrocarbon, Propellants, Explos., Pyrotech., 27(1), 1-6, 2002.

Dany.





[Edited on 9-10-2013 by Dany]

Attachment: Octanitrocubane A New Nitrocarbon.pdf (105kB)
This file has been downloaded 2457 times

APO - 9-10-2013 at 11:40

So, instead of that, could the reaction of Cubane 1,4-Dicarboxylic Chloride with Oxalyl Chloride be ommited to proceed with the next four steps to form 1,4-Dinitrocubane? That way ring cleavage could be avoided? If yes, then could the 1,4-Dinitrocubane then undergo interfacial nitration to Heptanitocubane and so on?

If that's not an option, traditional synthesis routes are way to lenghty, but if I were able to replicate the JC Barborak synthesis up to the formation of 1,3-Cubane Dicarboxylic Acid and add enough Oxalyl Chloride, according to the conversion pathways here it would form 1,3,5,7 Cubane Tetracarboxylic Chloride, which would work perfectly for stages 9-14 on my synthesis diagram.

Now, how would I make or get Cyclobutadieneiron Tricarbonyl and 2,5-Dibromobenzoquinone?

Dany - 9-10-2013 at 12:06

well...2,5-Dibromobenzoquinone can be bought from TCI chemicals (TCI sell chemical to laboratory, i don't know if they accept to send items to individual)

http://www.tcichemicals.com/eshop/fr/eu/commodity/D2249/

Cyclobutadieneiron Tricarbonyl:

http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv6...

(and references therein)

Dany.

APO - 9-10-2013 at 14:59

I found this for 2,5-Dibromobenzoquinone starting from 1,4-Benoquinone:

<img src="http://apo.comule.com/2,5-Dibromohydroquinone.png" width="660" height="340">

1,4-Benzoquinone is reacted with Hydrobromic Acid to form 2,5-Dibromohydroquinone.


<img src="http://apo.comule.com/2,5-Dibromobenzoquinone.png" width="450" height="200">

2,5-Dibromohydroquinone is reacted with Ceric Ammonium Nitrate to form 2,5-Dibromobenzoquinone.


Certainly preferable to paying two hundred dollars to TCI for two grams of the stuff, considering you can make more than a pound for that price.


Any easier synthesis for Cyclobutadieneiron Tricarbonyl though?

APO - 11-10-2013 at 18:05

For the Cyclobutadieneiron Tricarbonyl, I haven't found any alternative synthesis route other than what's found on Orgsyn and Wikipedia.

Meanwhile, this patent says that Cubane-1,4-dicarboxylic Acid can be converted to 1,3,5,7-Tetranitrocubane by

Quote:

photolyzing a solution of cubane-1,4-dicarboxylic acid, oxalyl chloride, and methanol under a sunlamp to form 1,3,5,7-tetramethoxycarbonylcubane. The 1,3,5,7-tetramethoxycarbobnylcubane is refluxed with diphenylphosphoryl azide and triethylamine in tert-butyl alcohol to form 1,3,5,7-tetra[(tert-butoxycarbonyl)-amino]cubane. The 1,3,5,7-tetra[(tert-butoxycarbonyl)-amino]cubane is hydrolyzed and decarboxylated to the form 1,3,5,7-tetraamino cubane. The 1,3,5,7-tetraamino cubane is refluxed with m-chloroperbenzoic acid and 4,4′-thiobis(2-tert-butyl-6-methylphenol) in dichloroethane to yield 1,3,5,7-tetranitrocubane


Is this right? How is the fourth position swapped like that? According to the conversion pathways of Cubane Carboxylic Chloride here, Cubanes with Carboxylic Chloride groups on both postions one and four, follow a very strict path way on group addition that leads directly to 1,2,4 and then 1,2,4,7 positions.

Also, still no answer on if 1,4-Dinitrocubane could undergo interfacial nitration all the way up to Heptanitrocubane. I mean, do you really need to start from Tetranitrocubane? Why isn't a less nitrated form suitable for interfacial nitration?